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Chapter 8—Molecular Structure and Covalent Bonding Theories
MULTIPLE CHOICE
1. The electrons in the outer shell of an atom are involved in bonding. Another name for the outer shell is
____.
a. valence shell
b. bonding shell
c. hybridized shell
d. VSEPR shell
e. Lewis shell
ANS: A
OBJ: Define valence shell.
TOP: Valence Electrons
2. The valence shell is

a. the highest energy level occupied by electrons.
b. the set of orbitals used to make triple bonds.
c. the orbitals belonging to the entire molecule.
d. the lowest energy level occupied by electrons.
e. the hard covering on crustaceans.
ANS: A
OBJ: Define valence shell.
TOP: Valence Electrons
3. What is the electronic geometry for 6 regions of high electron density on a central atom?
a. octahedral
b. square planar
c. tetrahedral
d. trigonal bipyramidal
e. trigonal planar
ANS: A
OBJ: Identify the electron geometry given the number of electron groups surrounding the central
atom.
TOP: Valence Shell Electron Pair Repulsion (VSEPR) Theory
4. Which of the following do not count as regions of high electron density with respect to the central
atom in a molecule?
a. single bonds
b. lone pairs on an outer atom
c. lone pairs on the central atom
d. double bonds
e. triple bonds
ANS: B
OBJ: Identify electron groups which define the electron geometry around the central atom.
Whitten 10e Test Bank 1

5. The electronic geometry is
a. the arrangement of atoms around the central atom in a molecule.
b. the arrangement of H atoms around the central atom in a molecule.
c. the arrangement of regions of high electron density around the central atom in a molecule.
d. the arrangement of lone pairs around the central atom in a molecule.
e. the sets of quantum numbers for a central atom.
ANS: C
OBJ: Define electron geometry.
6. What is the electronic geometry for 3 regions of high electron density on a central atom?
a. octahedral
b. square planar
c. trigonal bipyramidal
d. tetrahedral
e. trigonal planar
ANS: E
OBJ: Identify the electron geometry given the number of electron groups surrounding the central
atom.
7. What angle(s) are associated with a central atom that has trigonal bipyramidal electronic geometry?
a. 109.5
b. 120
c. 120 and 180
d. 90 and 120
e. 90 and 180
ANS: D
OBJ: Identify the angles between electron groups given the electron geometry.
8. What angle(s) are associated with a central atom that has tetrahedral electronic geometry?
a. 109.5
b. 120
c. 120 and 180
d. 90 and 120
e. 90 and 180
ANS: A
OBJ: Identify the angles between electron groups given the electron geometry.
9. The phosphorus pentachloride molecule is nonpolar and contains no lone (unshared) electron pairs on
the phosphorus atom. What are all of the possible Cl−P−Cl bond angles?
a. 120
b. 180
c. 109.5
d. 90, 120, and 180
e. 90 and 180

ANS: D
OBJ: Identify the angles between electron groups given the molecule name, polarity, and number of
lone pairs on the central atom.
10. Which of the following is not one of the basic ideas of the VSEPR theory?
a. Each electron group in the valence shell of a central atom is significant.
b. The groups of valence shell electrons on the central atom repel one another.
c. The groups of valence shell electrons are arranged about the central atom so that the
repulsions among them are as small as possible.
d. The electron groups have maximum separation about the central atom.
e. The number of electron groups is determined by counting the number of lone pairs and the
total number of bonds.
ANS: E
OBJ: Identify the tenets of VSEPR theory.
11. Which of the following statements concerning polar molecules is false?

a. There must be at least one polar bond or one unshared pair of electrons on the central
atom.
b. If there are more than one polar bond, they must not be symmetrically arranged so that
their polarities cancel.
c. If there are more than one unshared pair of electrons on the central atom, they must not be
symmetrically arranged so that their polarities cancel.
d. There must be an odd number of polar bonds so that their polarities not cancel.
e. A molecule with symmetrically arranged polar bonds can be polar if the central atom is
bonded to atoms of different elements.
ANS: D
OBJ: Identify the factors that give polar or nonpolar molecules.
TOP: Polar Molecules: The Influence of Molecular Geometry
12. Which one of the following molecules is polar?

a. N2
b. P4
c. Cl2
d. CO2
e. H2O
ANS: E
OBJ: Identify the polar molecule.
13. Which one of the following molecules is nonpolar?

a. H2O
b. CO2
c. CSO
d. NF3
e. NH3
ANS: B
OBJ: Identify the nonpolar molecule.

14. CH4 is a nonpolar molecule. Which of the following similar molecules is also nonpolar?
a. CH3Cl
b. CH2Cl2
c. SiH3Cl
d. SiH4
e. SiH2Cl2
ANS: D
15. Draw the dot formula for the HNO2 molecule. The nitrogen atom is the central atom and the hydrogen
atom is attached to an oxygen atom. On the basis of the number of regions of high electron density
about the nitrogen atom, predict the nitrogen atom hybridization.
a. sp
b. sp2
c. sp3
d. sp3d
e. sp3d2
ANS: B
OBJ: Determine the central atom hybridization given the formula.
TOP: Valence Bond (VB) Theory
16. Draw the dot formula for the HNO2 molecule. The nitrogen atom is the central atom and the hydrogen
atom is attached to an oxygen atom. On the basis of the number of regions of high electron density
about the nitrogen atom, what is (are) the approximate bond angle(s) about the N atom?
a. 180
b. 90
c. 120
d. 120 and 90
e. 109
ANS: C
17. Which one of the following statements about compounds or polyatomic ions of the A group elements
is false?
a. All compounds in which the central atom is sp3d2 hybridized violate the octet rule.
b. Sulfur hexafluoride is an example of a compound with a central atom that has sp3d2
hybridization.
c. All molecules in which the central element is sp3d2 hybridized have octahedral electronic
geometry.
d. All molecules in which the central element is sp3d2 hybridized have octahedral molecular
geometry.
e. All ions in which the central atom is sp3d2 hybridized have octahedral electronic geometry.
ANS: D
DIF: Harder Question
OBJ: Understand the connection between valence bond theory and VSEPR theory.

18. Which of the following statements about the valence bond theory is false?
a. For an atom to share more than 8 electrons it must hybridize d orbitals.
b. To make 4 single bonds, an atom will make 4 sp3 hybrid orbitals.
c. The number of hybrid orbitals formed equals the number of high electron density regions.
d. Trigonal planar molecules use sp2 hybrid orbitals
e. Atoms that do not complete their octet use either sp3d or sp3d2 hybrid orbitals.
ANS: E
19. Which response contains all the following statements that are true, and no others?
I. A set of sp2 orbitals can be thought of as one s orbital one-third of the time and two p
orbitals two-thirds of the time.
II. A set of sp orbitals can accommodate a maximum of six electrons.
III. The orbitals resulting from sp3d2 hybridization are directed toward the corners of an
octahedron.
IV. A set of sp3 orbitals results from the mixing of one s orbital and three p orbitals.
a. II and IV
b. I, II, and IV
c. II, III, and IV
d. III and IV
e. all are true
ANS: D
20. The hybridization associated with the central atom of a molecule in which all the bond angles are 180
is ____.
a. sp
b. sp2
c. sp3
d. sp3d
e. sp3d2
ANS: A
OBJ: Identify the central atom hybridization given the bond angles.
21. The hybridization associated with the central atom of a molecule in which all the bond angles are
109.5 is ____.
a. sp
b. sp2
c. sp3
d. sp3d
e. sp3d2
ANS: C
OBJ: Identify the central atom hybridization given the bond angles.

22. The bond angle(s) associated with sp3d2 hybridization is (are) ____.
a. 90 and 180
b. 120
c. 109
d. 90 and 120
e. 109 and 120
ANS: A
OBJ: Identify the bond angles given the central atom hybridization.
23. The central atom in a molecule is bonded to 3 other atoms and has 2 lone pairs. What type of hybrid
orbitals are formed by the central atom?
a. sp
b. sp2
c. sp3
d. sp3d
e. sp3d2
ANS: D
OBJ: Identify the central atom hybridization given the number of atoms and lone pairs attached to the
central atom.
24. The central atom in a molecule is sharing a total of 12 electrons. What type of hybrid orbitals are
formed by the central atom?
a. sp
b. sp2
c. sp3
d. sp3d
e. sp3d2
ANS: E
OBJ: Identify the central atom hybridization given the number electrons shared by the central atom.
25. The central atom in a molecule has three regions of high electron density. What type of hybrid orbitals
are formed by the central atom?
a. sp
b. sp2
c. sp3
d. sp3d
e. sp3d2
ANS: B
OBJ: Identify the central atom hybridization given the number of electron groups around the central
atom.

26. The O−N−O bond angles associated with the nitrate ion, NO3−, are all 120. The hybridization at the
nitrogen atom is ____.
a. sp2
b. sp3
c. sp3d2
d. sp
e. sp3d
ANS: A
OBJ: Identify the central atom hybridization given the bond angles around the central atom.
27. Which of the following statements about polar molecules is false?

a. A molecule with polar bonds can be nonpolar.
b. A molecule with polar bonds can be polar.
c. A molecule with only nonpolar bonds can be polar.
d. A molecule with 120 bond angles can be polar.
e. A molecule with 180 bond angles can be polar.
ANS: C
OBJ: Understand the connection between molecular geometry, polar bonds, and polarity of a
molecule.
28. Consider the BeCl2 molecule. Which statement about this molecule is false?
a. The molecule is linear.
b. The molecule has polar bonds.
c. The molecule is polar.
d. The central atom is sp hybridized.
e. Be does not satisfy the octet rule.
ANS: C
OBJ: Apply VSEPR and VB theory given the formula.
TOP: Linear Electronic Geometry: AB2 Species
29. Which one of the following molecules has sp hybridization at the central atom?
a. BeF2
b. SeF6
c. BF3
d. PF5
e. CF4
ANS: A
OBJ: Identify the formula consistent with the given central atom hybridization.
30. What is (are) the bond angle(s) in BeI2 molecules?

a. 120
b. 180
c. 90 and 180
d. 120 and 90
e. 109

ANS: B
OBJ: Determine the molecule bond angles given the formula.
31. Cadmium iodide, CdI2, is a covalent compound. The molecule has the same geometry as a BeCl2
molecule. Which of the following kinds of hybrid orbitals does the cadmium atom likely utilize in
CdI2?
a. sp
b. sp2
c. sp3
d. sp3d
e. sp3d2
ANS: A
32. Which of the following statements concerning HgI2 (a covalent compound) is false?
a. HgI2 is a linear molecule.
b. The hybridization of the central Hg atom is sp.
c. The electronegativity difference between Hg and I is so large that HgI2 is an ionic
compound.
d. Because the bond angle is 180, the two bond dipoles cancel to give a nonpolar molecule.
e. The Hg atom in HgI2 does not satisfy the octet rule.
ANS: C
OBJ: Apply VSEPR and VB theory given the formula. | Understand the difference between ionic and
covalent.
33. What kind of hybrid orbitals are utilized by the boron atom in BF3 molecules?
a. sp
b. sp2
c. sp3
d. sp3d
e. sp3d2
ANS: B
OBJ: Identify the central atom hybridization given the formula.
TOP: Trigonal Planar Electronic Geometry
34. What is the hybridization at the boron atom in gaseous BBr3?

a. sp3d
b. sp
c. sp2
d. sp3
e. sp3d2
ANS: C

35. Which of the following molecules has 120 bond angles?
a. BeI2
b. CH4
c. H2S
d. BCl3
e. NF3
ANS: D
OBJ: Identify the formula consistent with the given bond angles.
36. Which of the following molecules has 120 bond angles?

a. BF4−
b. CF4
c. H2O
d. BI3
e. NH4+
ANS: D
37. Which one of the following molecules has only 120 bond angles?
a. PF3
b. SF6
c. BI3
d. PF5
e. NF3
ANS: C
38. Which one of the following molecules has a central atom that is sp2 hybridized?
a. BeF2
b. BCl3
c. PCl3
d. H2O
e. NH3
ANS: B
39. Which of the following is a false statement about BF3?

a. BF3 has trigonal planar molecular geometry.
b. BF3 has trigonal pyramidal electronic geometry.
c. All three bond angles in BF3 are 120.
d. The B atom does not satisfy the octet rule.
e. Although the electronegativity difference between B and F is large (2.0 units), BF3 is a
covalent compound.
ANS: B

40. Consider the following statements about BCl3 molecules. Which statement is false?
a. The B−Cl bonds are quite polar.
b. The bond dipoles exactly cancel.
c. The Cl−B−Cl bond angles are 109.5.
d. BCl3 molecules are nonpolar.
e. BCl3 molecules are planar.
ANS: C
41. What kind of hybrid orbitals are utilized by the carbon atom in CF4 molecules?
a. sp
b. sp2
c. sp3
d. sp3d
e. sp3d2
ANS: C
TOP: Tetrahedral Electronic Geometry: AB4 Species
42. What is the hybridization at the central atom in SiH4?

a. sp
b. sp2
c. sp3
d. sp3d
e. sp3d2
ANS: C
43. Consider a molecule with 109.5 bond angles and sp3 hybridization at the central atom. Which of the
following molecules does not fit this description?
a. CH3Cl
b. SiF4
c. SF4
d. SiCl4
e. CF4
ANS: C
OBJ: Identify the formula consistent with the given bond angles and central atom hybridization.
44. Consider CH4 and CF4. Electronegativities: C = 2.5, H = 2.1, F = 4.0. Which statement is false?
a. Both are sp3 hybridized at carbon.
b. The bond angles in CF4 are smaller than those in CH4.
c. The C−F bonds are more polar than the C−H bonds.
d. Both molecules are nonpolar.
e. The bond dipoles in CF4 are directed toward the fluorine, but those in CH4 are directed
toward the carbon atom.

ANS: B
45. Which statement concerning the ion, SO42−, is true?

a. The ion's charge results in there being one lone pair of electrons on the S atom.
b. There are five regions of high electron density on the S atom.
c. The bond angles are 90.
d. The electronic geometry is octahedral.
e. The hybridization of the S atom is sp3.
ANS: E
46. Which of the following statements about chloroform, CHCl3, is false?

a. The hybridization of C is sp3.
b. The hybridization of Cl is sp3.
c. The bond angles are 109.5.
d. The molecule is polar.
e. The molecule has tetrahedral electronic geometry.
ANS: B
47. Which response contains all the characteristics listed that should apply to silicon tetrafluoride, SiF4,
and no other characteristics?
I. tetrahedral
II. 120 bond angles
III. sp hybridized at C
IV. polar molecule
V. one unshared pair of electrons on Si
a. II and III
b. I
c. I and V
d. II, IV, and V
e. none of these
ANS: B

a. BCl3
b. CdI2
c. CCl4
d. NCl3
e. BeBr2
ANS: D
OBJ: Identify the formula consistent with a polar molecule.

a. BeCl2
b. BCl3
c. BF4−
d. CH2F2
e. CF4
ANS: D
50. Which one of the following molecules is nonpolar?

a. CCl4
b. CH2Cl2
c. CH3Cl
d. CHCl3
e. SiH2Cl2
ANS: A
OBJ: Identify the formula consistent with a nonpolar molecule.

a. BCl3
b. BeI2
c. CCl4
d. CHCl3
e. Br2
ANS: D
52. Molecules such as NF3 are best described by assuming what kind of hybridization at the central atom?
a. sp
b. sp2
c. sp3
d. sp3d
e. sp3d2
ANS: C
TOP: Tetrahedral Electronic Geometry: AB3U Species
53. What is the hybridization of the nitrogen atom in NH3?

a. sp
b. sp2
c. sp3
d. sp3d
e. sp3d2
ANS: C

54. What is the hybridization of the sulfur atom in SO32−?
a. sp
b. sp2
c. sp3
d. sp3d
e. sp3d2
ANS: C
55. For AsF3, the electronic geometry is ____ and the molecular geometry is ____.
a. tetrahedral; trigonal planar
b. trigonal planar; tetrahedral
c. tetrahedral; tetrahedral
d. trigonal planar; trigonal planar
e. trigonal planar; linear
ANS: A
OBJ: Identify the central atom electron and molecular geometry given a formula.
56. The electronic geometry of the central atom in PCl3 is ____.

a. pyramidal
b. trigonal planar
c. tetrahedral
d. octahedral
e. trigonal bipyramidal
ANS: C
OBJ: Identify the central atom electron geometry given a formula.
57. The molecular geometry of PCl3 is ____.

a. pyramidal
b. trigonal planar
c. tetrahedral
d. octahedral
ANS: A
OBJ: Identify the central atom molecular geometry given a formula.
58. Four of the following statements about the ammonia molecule, NH3, are correct. One is not. Which
one?
a. The ammonia molecule is tetrahedral.
b. Since nitrogen is more electronegative than hydrogen, the bond dipoles are directed
toward the nitrogen atoms.
c. The bond dipoles re-enforce the effect of the unshared pair of electrons on the nitrogen
atom.
d. The bond angles in the ammonia molecule are less than 109.
e. The nitrogen atom can be described as utilizing sp3 hybrid orbitals in the ammonia
molecule.

ANS: A
59. Which statement for NH3 and NF3 is false? Electronegativities: N = 3.0, H = 2.1, F = 4.0.
a. Both are sp3 hybridized at nitrogen.
b. The bond angles in NF3 are smaller than those in NH3.
c. The NF3 molecule is more polar than the NH3 molecule.
d. Both molecules have one unshared pair of electrons in the outer shell of nitrogen.
e. The bond dipoles of NF3 are directed toward fluorine, whereas those in NH3 are directed
toward nitrogen.
ANS: C
60. Four of the following statements about the ammonia molecule, NH3, and the nitrogen trifluoride
molecule, NF3, are correct. One is not. Which one?
a. The NH3 molecule is more polar than the NF3 molecule.
b. The bond dipoles in NF3 are directed toward the more electronegative fluorine atoms.
c. The bond dipoles in NF3 oppose the effect of the unshared pair of electrons.
d. The nitrogen atom can be described as utilizing sp3 hybrid orbitals in the nitrogen
trifluoride molecule.
e. Fluorine atoms are larger than hydrogen atoms, and therefore the bond angles in NF3 are
greater than in NH3.
ANS: E
61. Which of the following statements about PBr3 is false?

a. It is a polar molecule.
b. The P−Br bonds are polar
c. P is sp3 hybridized.
d. The bond angles are slightly larger than 109.5.
e. P has one lone pair.
ANS: D
62. Which one of the following is a nonpolar molecule with polar covalent bonds?
a. NH3
b. H2Te
c. SOCl2 (S is central atom)
d. BeBr2
e. HF
ANS: D

63. Which one of the following is a nonpolar molecule with polar bonds?
a. H2O
b. NH3
c. PF5
d. CHCl3
e. none of these
ANS: C
64. The molecular geometry of the hydrogen sulfide molecule is ____.

a. linear
b. angular
c. trigonal planar
d. pyramidal
ANS: B
OBJ: Identify the central atom molecular geometry given the molecule name.
TOP: Tetrahedral Electronic Geometry: AB2U2 Species
65. Many simple molecules contain two lone pairs of electrons (unshared pairs) that occupy hybrid
orbitals on the central element. Which of the following kinds of electron-electron repulsions are
smallest in such molecules?
a. bonding pair-bonding pair
b. bonding pair-lone pair
c. lone pair-lone pair
d. depends on hybrid orbitals
e. repulsions between all types of pairs of electrons are the same
ANS: A
OBJ: Identify the weakest electron repulsions.
66. Many simple molecules contain lone pairs of electrons (also referred to as unshared pairs) which
occupy hybrid orbitals of the central element in a molecule. If an atom of the central element utilizes
sp3 hybrid orbitals in a compound, which one of the following types of repulsions would be greater?
a. bonding pair-bonding pair
b. bonding pair-lone pair
c. lone pair-bonding pair
d. lone pair-lone pair
e. repulsions between all types of pairs of electrons are the same
ANS: D
OBJ: Identify the weakest electron repulsions.

67. Which response contains all of the following molecules that can be described as bent or angular
molecules and none that have other shapes?
BeI2, SO2, H2S, PF3, CO2
a. SO2, H2S
b. BeI2, SO2
c. BeI2, PF3, CO2
d. PF3, CO2
e. another combination
ANS: A
OBJ: Apply VSEPR theory given formulas.
68. Which of the following molecules has the smallest bond angle(s)?
a. CH4
b. NH3
c. H2O
d. CF4
e. CO2
ANS: C
OBJ: Identify the formula consistent with the smallest bond angle.
69. What is the hybridization of the oxygen atom in H3O+?

a. sp
b. sp2
c. sp3
d. sp3d
e. sp3d2
ANS: C
70. Which of the following molecules is sp3 hybridized at the central atom and has bent molecular
geometry?
a. CH2Cl2
b. NH3
c. SO2
d. OF2
e. CO2
ANS: D
OBJ: Identify the formula consistent with the given central atom hybridization and molecular
geometry.

71. Which statement about the water molecule is incorrect?
a. The decrease in bond angle from the tetrahedral angle (109.5) is greater for H2O than for
NH3.
b. The bond angle for H2O is smaller than for NH3 because of the lone pair-lone pair
repulsion in H2O.
c. The water molecule is very polar.
d. The effect of the very polar bonds in water is canceled by the effect of the 2 lone pairs of
electrons.
e. The O atom is sp3 hybridized.
ANS: D
OBJ: Apply VSEPR and VB theory given the molecule name.
72. Consider the chlorine atom in the HCl molecule. Which statement below is true?
a. The chlorine atom has tetrahedral electronic geometry.
b. The molecule is angular.
c. The molecule is nonpolar.
d. VSEPR theory and VB theory disagree about the molecular geometry of HCl.
e. All of these are true.
ANS: A
OBJ: Apply VSEPR theory given the formula.
TOP: Tetrahedral Electronic Geometry: ABU3 Species
73. An element that is sp3d hybridized and which has no lone pairs of electrons around it in a molecule is
at the center of a(n) ____ described by imaginary lines connecting the identical surrounding atoms.
a. triangular plane
b. tetrahedron
c. octahedron
d. pyramid
e. trigonal bipyramid
ANS: E
OBJ: Identify the molecular geometry given the central atom hybridization and central atom lone
pairs.
TOP: Trigonal Bipyramidal Electronic Geometry: AB5, AB4U, AB3U2, and AB2U3
74. What is the hybridization at arsenic in AsF5 molecules?

a. sp
b. sp2
c. sp3
d. sp3d
e. sp3d2
ANS: D
OBJ: Identify the central atom electron geometry given a formula.
75. What is the hybridization at the central atom (P) of PF3Cl2?

a. sp
b. sp2
c. sp3
d. sp3d
e. sp3d2

ANS: D
76. Which one of the following molecules has sp3d hybridization at the central atom?
a. PF5
b. NH3
c. SF6
d. HF
e. CF4
ANS: A
77. How many unshared electrons are there in the highest energy level of phosphorus in the covalent
compound PF5? (HINT: Draw Lewis dot formula.)
a. eight
b. two
c. three
d. none
e. five
ANS: D
OBJ: Determine the number of central atom lone pairs given a formula.
78. Which of the following statements about AsF5 is false?

a. The electronic geometry is trigonal bipyramidal.
b. As is sp3d hybridized.
c. As has one lone pair.
d. Bonding angles are 90, 120 or 180.
e. The molecular geometry is trigonal bipyramidal.
ANS: C
79. The PF5 molecule exists whereas NF5 does not. Which one of the following is the best explanation for
this fact?
a. Phosphorus atoms can undergo hybridization involving d orbitals, whereas nitrogen atoms
cannot.
b. The first five ionization energies of nitrogen are too high but those of phosphorus are not.
c. The electron affinity of nitrogen is too high.
d. NF5 would be too polar to be stable.
e. Simple P5+ ions exist but simple N5+ ions are too small to exist.
ANS: A
OBJ: Apply a controversial interpretation of VBT in rationalizing experimental data.

80. Which of the following statements about SCl4 is false?
a. The electronic geometry is trigonal bipyramidal.
b. S is sp3d hybridized.
c. S has one lone pair.
d. Bonding angles are 90, 120 or 180.
e. The molecular geometry is trigonal bipyramidal.
ANS: E
81. What is the hybridization of the central I atom in I3−?

a. sp
b. sp2
c. sp3
d. sp3d
e. sp3d2
ANS: D
82. Which of the following molecules has three lone pairs of electrons on the central atom?
a. XeF4
b. SF4
c. SF6
d. XeF2
e. NCl3
ANS: D
83. Which of the following species has trigonal bipyramidal electronic geometry and trigonal bipyramidal
molecular geometry?
a. SF4
b. BrF3
c. I3−
d. XeF2
e. AsCl5
ANS: E
OBJ: Identify the formula consistent with the given central atom electron and molecular geometry.
84. Consider the SeF4 molecule. Where is (are) the lone pair(s) located on the central atom?
a. In the axial position.
b. In the equatorial position.
c. In two octahedral positions at 180 angles from each other.
d. In either axial or equatorial positions.
e. There are no lone pairs present in SeF4.
ANS: B
OBJ: Identify the location of any central atom lone pairs given the molecule formula.

85. Which one of the following is a polar molecule with nonpolar bonds?
a. H2O
b. NH3
c. PF5
d. CHCl3
e. none of these
ANS: E
86. Which response includes all the polar molecules listed and no nonpolar molecules?
BCl3, AsF5, NF3, H2S
a. BCl3, AsF5
b. AsF5, NF3, H2S
c. NF3, H2S
d. BCl3, H2S
e. BCl3, NF3
ANS: C
OBJ: Identify the formulas of polar molecules.
87. Which one of the following is a polar molecule with nonpolar bonds?
a. H2O
b. NH3
c. PF5
d. CHCl3
e. none of these
ANS: E

a. AsF5
b. PCl3
c. CO2
d. CF4
e. SiH4
ANS: B
89. Which one of the following molecules has an octahedral electron geometry?
a. BeCl2
b. SeF6
c. BF3
d. PF5
e. CF4

ANS: B
OBJ: Identify the formulas that is not consistent with the given electron geometry.
TOP: Octahedral Electronic Geometry: AB6, AB5U, and AB4U2
90. Which of the following statements about molecules with octahedral electronic geometry is false?
a. They are sp3d2 hybridized.
b. The molecular geometry is square planar if there are two lone pairs of electrons on the
central atom.
c. The bond angles are 90, 120 or 180.
d. Octahedral geometry is symmetrical.
e. If there are two lone pairs of electrons on the central atom they will be 180 apart.
ANS: C
OBJ: Apply VSEPR and VB theory given the central atom electron geometry.
91. What is the hybridization at the central element in SeF6?

a. sp
b. sp2
c. sp3
d. sp3d
e. sp3d2
ANS: E
92. What is the hybridization at the sulfur atom in SF6?

a. sp
b. sp2
c. sp3
d. sp3d
e. sp3d2
ANS: E
93. Draw the dot formula for the noble gas compound xenon tetrafluoride, XeF4. What is the hybridization
of xenon?
a. sp
b. sp2
c. sp3
d. sp3d
e. sp3d2
ANS: E

94. Which of the following species has square planar molecular geometry?
a. CH4
b. SF4
c. XeF4
d. NH4+
e. SO42−
ANS: C
OBJ: Identify the formula consistent with given molecular geometry.
95. Which of the following species has square pyramidal molecular geometry?
a. PF5
b. NH4+
c. SbCl5
d. IF5
e. SiCl4
ANS: D
OBJ: Identify the formula consistent with given molecular geometry.
96. Which of the following species does not have octahedral electronic geometry?
a. IF4−
b. BrCl5
c. XeF4
d. PF6−
e. AsF5
ANS: E
OBJ: Identify the formulas that is not consistent with the given electron geometry.
97. The central atom of which of the following species does not have sp3d2 hybridization?
a. XeF4
b. SeF6
c. PF6−
d. IF7
e. ClF5
ANS: D
OBJ: Identify the formula not consistent with the given central atom hybridization.

a. SiH4
b. SF6
c. H2
d. PCl5
e. SF4
ANS: E

99. Which of the following statements about multiple bonds is true?
a. A double bond consists of two sigma bonds.
b. A sigma bond results from the side-on overlap of p atomic orbitals.
c. A pi bond results from the head-on overlap of p atomic orbitals.
d. sp2 hybridization in carbon is associated with one double bond and two single bonds.
e. sp3 hybridization in carbon is associated with one double bond and two single bonds.
ANS: D
OBJ: Understand the VBT interpretation of multiple bonds.
TOP: Compounds Containing Double or Triple Bonds
100. How many sigma () bonds and how many pi () bonds does the ethene molecule contain?
a. 4 , 2 
b. 5 , 2 
c. 5 , 1 
d. 5 , 0 
e. 8 , 2 
ANS: C
OBJ: Determine the number of sigma and pi bonds given the Lewis structure.
101. What is the hybridization of a carbon atom involved in a double bond?

a. sp
b. sp2
c. sp3
d. sp3d
e. sp3d2
ANS: B
OBJ: Identify the hybridization of an atom in a molecule given its bonding.
102. What is the geometry of a carbon atom involved in one double bond?
a. linear
b. trigonal planar
c. tetrahedral
e. octahedral
ANS: B
OBJ: Identify the geometry of an atom in a molecule given its bonding.

103. Choose the following false statement.
a. A sigma bond is a bond resulting from head-on overlap of atomic orbitals.
b. A pi bond is a bond resulting from side-on overlap of atomic orbitals.
c. A double bond consists of one sigma bond and one pi bond.
d. A triple bond may consist of one sigma bond and two pi bonds or of two sigma bonds and
one pi bond.
e. A carbon atom involved in a double bond may not be sp3 hybridized.
ANS: D
OBJ: Understand the VBT interpretation of covalent bonding.
TOP: Compounds Containing Triple Bonds
104. Which of the following statements regarding a carbon atom involved in 2 double bonds is false?
a. The geometry is linear.
b. The hybridization is sp.
c. There are 2 sigma and two pi bonds.
d. The C atom has two unhybridized p atomic orbitals.
e. The C atom can make one more bond to complete its octet.
ANS: E
OBJ: Apply the VBT interpretation of covalent bonding.
105. How many sigma () bonds and how many pi () bonds does the acetylene molecule contain?
a. 5  and 1 
b. 2  and 3 
c. 3  and 1 
d. 2  and 2 
e. 3  and 2 
ANS: E
OBJ: Determine the number of sigma and pi bonds given the molecule name.
106. What is the hybridization of a carbon atom involved in a triple bond?

a. sp
b. sp2
c. sp3
d. sp3d
e. sp3d2
ANS: A
OBJ: Identify the central atom hybridization given the bonding of an atom in a molecule.
107. What is the geometry of a carbon atom involved in a triple bond?

a. linear
b. trigonal planar
c. tetrahedral
e. octahedral
ANS: A
OBJ: Identify the central atom geometry given the bonding of an atom in a molecule.

108. Which of the following responses contains all of the true statements for ethyne?
I. The ethyne molecule has a double bond between its 2 carbon atoms.
II. The ethyne molecule has a triple bond between its 2 carbon atoms.
III. One pi bond is formed between the 2 carbon atoms by head-on overlap of the sp hybrid
orbitals.
IV. One sigma bond is formed between the 2 carbon atoms by head-on overlap of the sp2
hybrid orbitals.
V. The ethyne molecule is linear.
a. I and III
b. II and IV
c. I and IV
d. II and V
e. II and III
ANS: D
OBJ: Apply VSEPR and VB theory given the molecule name.
109. Choose the species that is incorrectly matched with the electronic geometry about the central atom.
Molecule / Electronic Geometry

a. CF4 / tetrahedral
b. BeBr2 / linear
c. H2O / tetrahedral
d. NH3 / tetrahedral
e. PF3 / pyramidal
ANS: E
OBJ: Determine if a formula is consistent with the given electron geometry.
TOP: A Summary of Electronic and Molecular Geometries

a. SiH4 / tetrahedral
b. SO2 / trigonal planar
c. NH2- / tetrahedral
d. NH3 / tetrahedral
e. BH4− / trigonal planar
ANS: E

a. PCl5 / trigonal bipyramidal
b. SF6 / octahedral
c. XeF2 / trigonal bipyramidal
d. XeF4 / octahedral
e. GeCl4 / trigonal bipyramidal

ANS: E
Ion / Electronic Geometry

a. NO2− / trigonal planar
b. ClO4− / tetrahedral
c. SO32− / pyramidal
d. ClO3− / tetrahedral
e. BrO4− / tetrahedral
ANS: C
113. Which molecule is incorrectly matched with the molecular geometry?
Molecule / Molecular Geometry

a. CCl4 / tetrahedral
b. PH3 / pyramidal
c. BeCl2 / linear
d. BBr3 / trigonal planar
e. SO2 / linear
ANS: E
OBJ: Determine if a formula is consistent with the given molecular geometry.

a. I3− / linear
b. BrF3 / T-shaped
c. BH4− / tetrahedral
d. SbCl5 / trigonal bipyramidal
e. NO2− / tetrahedral
ANS: E

a. SeF6 / octahedral
b. CCl4 / tetrahedral
c. SO3 / pyramidal
d. SF4 / tetrahedral
e. SbH3 / pyramidal

ANS: D

a. SF6 / octahedral
b. AsH3 / pyramidal
c. BCl3 / trigonal planar
d. AsF5 / trigonal bipyramidal
e. H2S / linear
ANS: E

a. SO32− / pyramidal
b. SO3 / trigonal planar
c. SO42− / tetrahedral
d. ClO3− / tetrahedral
e. ClO− / linear
ANS: D
118. Which one of the following pairs of molecules and molecular geometries is incorrectly matched?
Compound / Molecular Geometry

a. NF3 / pyramidal
b. H2O / angular
c. BF3 / trigonal planar
d. AsF5 / pentagonal planar
e. SeF6 / octahedral
ANS: D
119. Which one of the following pairs of molecules and molecular geometries is incorrectly matched?
Compound / Molecular Geometry

a. HBr / linear
b. CBr4 / tetrahedral
c. AsH3 / pyramidal
d. BeBr2 / angular
e. CH4 / tetrahedral
ANS: D

120. Which response includes all of the molecules listed that have the same molecular geometry as
electronic geometry, and only those molecules?
BCl3, AsF5, NF3, H2S
a. BCl3, AsF5
b. AsF5, NF3, H2S
c. NF3, H2S
d. BCl3, H2S
e. BCl3, NF3
ANS: A
OBJ: Identify the molecules with identical electron and molecular geometries, given the formulas.
121. Which one of the following molecules has a central atom that is not sp3 hybridized?
a. H2O
b. NH3
c. CH4
d. CHCl3
e. SF4
ANS: E
OBJ: Identify the formula not consistent with the given central atom hybridization.
122. Which of the following molecules does not have tetrahedral electronic geometry?
a. SF4
b. SO32−
c. ClO3−
d. ClO2−
e. CCl2F2
ANS: A
OBJ: Identify the formula not consistent with given electron geometry.
123. Which, if any, of the compounds listed are not sp3 hybridized at the central atom?
I. CF4
II. H2O
III. SiF4
IV. CHCl3
V. NH3
a. III and IV
b. I, II, and III
c. II, IV, and V
d. III and V
e. all are sp3 hybridized
ANS: E
OBJ: Identify the formulas not consistent with the given central atom hybridization.

124. Which, if any, of the compounds listed are not sp3d hybridized at the central atom?
I. BF3
II. AsI5
III. SF4
IV. BrF5
V. XeF4
a. III and IV
b. I, II, and III
c. I, IV, and V
d. III and V
e. all are sp3d hybridized
ANS: C
125. Which species is incorrectly matched with the hybridization at the central atom?
Species / Hybridization at Central Atom

a. SeF6 / sp3d
b. CO2 / sp
c. NH4+ / sp3
d. BCl3 / sp2
e. BeBr2 / sp
ANS: A
126. Which species is incorrectly matched with the hybridization at the central atom?
Species / Hybridization at Central Atom

a. SO2 / sp2
b. CF4 / sp3
c. PF5 / sp3d2
d. SeO42− / sp3
e. HCN / sp
ANS: C
127. Which species is incorrectly matched with bond angles?
Molecule / Bond Angles

a. SiCl4 / 109.5
b. BeI2 / slightly less than 109
c. SF6 / 90 (and 180)
d. AsF5 / 90, 120 (and 180)
e. BF3 / 120
ANS: B
OBJ: Identify the formulas not consistent with the given bond angles.


a. CI4 / 109.5
b. BeF2 / 180
c. HI / 90
d. I3− / 180
e. BI3 / 120
ANS: C

a. HCl / 180
b. ClO3− / slightly less than 109
c. NH3 / 107
d. SeO4− / 109.5
e. SnCl4 / 90, 120 (and 180)
ANS: E

a. NCl3 / 120
b. BeBr2 / 180
c. CCl4 / 109.5
d. PCl5 / 120 and 90 (and 180)
e. SeF6 / 90 (and 180)
ANS: A
131. What is the molecular geometry around an atom in a molecule or ion which is surrounded by
two lone pairs of electrons and two single bonds.
a. bent
b. trigonal pyramidal
c. tetrahedral
d. linear
e. trigonal planar
ANS: A DIF: easy
OBJ: Identify the central atom molecular geometry given the number of lone pairs and bonds.

132. What is the electron geometry (or electron arrangement) around an atom in a molecule or ion
which is surrounded by one lone pair of electrons and four single bonds.
a. trigonal bipyramidal
b. see-saw or distorted tetrahedron
c. T-shaped
d. linear
e. trigonal planar
ANS: A
DIF: easy
OBJ: Determine the electron geometry given the number of lone pairs and bonding pairs around the
central atom.
133. What is the bond angle in a trigonal planar molecule or ion?

a. 109°
b. 180°
c. 90°
d. 72°
e. 120°
ANS: E DIF: easy
OBJ: Identify the bond angle of a particular molecular geometry.
134. What is the molecular geometry around the nitrogen atom?
a. trigonal pyramidal
b. bent
c. tetrahedral
d. see-saw or distorted tetrahedral
e. trigonal planar
ANS: A
DIF: moderate
OBJ: Determine the molecular geometry around an atom given the Lewis structure.

135. When an atom in a molecule or ion is described as sp hybridized, its molecular geometry is
a. linear.
b. octahedral.
c. trigonal bipyramidal.
d. tetrahedral.
e. trigonal planar.
ANS: A
DIF: easy
OBJ: Determine the molecular geometry given the central atom hybridization.
136. Which of the labeled carbons (C1-C4) is sp-hybridized?
a. carbon three
b. carbon one
c. carbon two and four
d. carbon two
e. carbon one and three
ANS: A DIF: easy

OBJ: Identify the atom in the Lewis structure with the specified hybridization.
137. Which of the following molecules is nonpolar?
a. phosphorus trifluoride, PF3

b. sulfur tetrafluoride, SF4
c. hydrogen fluoride, HF
d. boron trifluoride, BF3
e. sulfur dioxide, SO2
ANS: D
DIF: moderate
TOP: Polar and Nonpolar Molecules

138. How many sigma and pi bonds are in the molecule pictured below?
a. thirteen sigma bonds and one pi bond

b. eleven sigma bonds and two pie bonds
c. thirteen sigma bonds and two pie bonds
d. eleven sigma bonds and five pie bonds
e. five sigma bonds and eleven pie bonds
ANS: A
DIF: easy
OBJ: Determine the number of sigma and pi bonds in the molecule given the Lewis structure.
139. What is the electron geometry around the nitrogen atom?
a. tetrahedral
b. trigonal planar
c. trigonal pyramidal
d. T-shaped
ANS: A
DIF: moderate
OBJ: Determine the electron geometry of the specified atom given the Lewis structure.
140. What is the electron geometry around carbon atom C2?

a. trigonal planar
b. linear
c. tetrahedral
d. trigonal pyramidal
e. bent
ANS: B
DIF: moderate
OBJ: Determine the molecular or electron geometry around the specified atom given the Lewis
structure.
141. What is the shape (molecular geometry) of PCl3?

a. trigonal planar
b. bent
d. tetrahedral
ANS: C
142. What is the shape (molecular geometry) of XeO3?

a. trigonal planar
d. seesaw
e. bent
ANS: B
143. What is the shape (molecular geometry) of IBr3?

a. trigonal planar
d. T-shaped
e. seesaw
ANS: D
Use the following Lewis structure for acetic acid to answer the following questions:

144. The ideal value for the H-C-H bond angle about atom 1 is:
a. 60o b. 90o c. 109.5o d. 120o e. 180o
ANS: C
OBJ: Identify the ideal bond angle.
145. The geometry about atom 3 is:

a. linear
b. bent
c. trigonal planar
d. tetrahedral
e. trigonal pyramidal
ANS: B
OBJ: Identify the geometry around a certain atom in a structural formula.
Use the following Lewis structure for acetamide to answer the following questions:
146. The ideal value for the C-C-N bond angle around atom 2 is:
a. 60o b. 90o c. 109.5o d. 120o e. 180o
ANS: D
147. The ideal value for the C-N-H bond angle around atom 3 is:
a. 60o b. 90o c. 109.5o d. 120o e. 180o
ANS: C
148. Draw the Lewis structure for SiH4 to decide whether it is polar or nonpolar.
a. polar b. nonpolar
ANS: B
NAT: Draw the Lewis structure given the formula and infer the molecule polarity from the Lewis
structure.
149. Draw the Lewis structure for SbF3 to decide whether it is polar or nonpolar.
a. polar b. nonpolar
ANS: A
OBJ: Draw the Lewis structure given the formula and infer the molecule polarity from the Lewis
structure.

150. What does the following figure represent?
a. the overlap of two 2p orbitals to form a pi bond

b. the overlap of two 2p orbitals to form a sigma bond
c. the overlap of two 1s orbitals to form a pi bond
d. the overlap of a 1s orbital and a 2p orbital to form a sigma bond
e. the overlap of a 1s orbital and a 2p orbital to form a pi bond
ANS: B
OBJ: Identify the correct description of sigma orbital overlap.
a. the overlap of two 2p orbitals to form a pi bond

b. the overlap of two 2p orbitals to form a sigma bond
c. the overlap of two 1s orbitals to form a pi bond
d. the overlap of a 1s orbital and a 2p orbital to form a sigma bond
e. the overlap of a 1s orbital and a 2p orbital to form a pi bond
ANS: D
a. the overlap of two 1s orbitals to form a pi bond

b. the overlap of two 1s orbitals to form a sigma bond
c. the overlap of two 2p orbitals to form a sigma bond
d. the overlap of a 1s orbital and a 2s orbital to form a sigma bond
e. the overlap of a 1s orbital and a 2s orbital to form a pi bond
ANS: A

153. What type of hybridization is represented in the figure below?
a. sp b. sp2 c. sp3 d. sp3d e. sp3d2

ANS: E
OBJ: Identify the hybrid orbital.

ANS: C

ANS: B

ANS: D

157. A molecule has sp3d2 hybridization with 1 lone pair. What is the geometry of this molecule?
a. trigonal bipyramidal
b. see saw
c. T-shaped
d. octahedral
e. square pyramidal
ANS: E
OBJ: Determine the molecular geometry given the hybridization and number of lone pairs.
158. A molecule has sp3 hybridization with 1 lone pair. What is the geometry of this molecule?
a. tetrahedral
b. trigonal planar
d. bent
ANS: C
OBJ: Determine the molecular geometry given the hybridization and number of lone pairs.
159. How many  and  bonds does C have in HCN?

a. 1  and 1  b. 1  and 2  c. 2  and 1  d. 2  and 2  e. 3  and 1 
ANS: D
OBJ: Determine the number of sigma and pi bonds given the formula.
160. If an atom has sp2 hybridization in a molecule, what is the maximum number of  and 
bonds that the atom can form?
ANS: A
OBJ: Determine the maximum number of sigma and pi bonds possible given the hybridization.
161. If an atom has sp hybridization in a molecule, what is the maximum number of  and  bonds
that the atom can form?
ANS: D
OBJ: Determine the maximum number of sigma and pi bonds possible given the hybridization.

SHORT ANSWER
Use the figures below to answer the following questions:
A B C D E
1. Which of the figures represents sp hybridization?
ANS: A
OBJ: Identify the correct hybridized orbital.
2. Which of the figures represents sp2 hybridization?
ANS: B
3. Which of the figures represents sp3 hybridization?
ANS: C
4. Which of the figures represents sp3d hybridization?
ANS: D
5. Which of the figures represents sp3d2 hybridization?
ANS: E
CONCEPTUAL
1. The actual bond angle in the water molecule is about 104. Discuss the likelihood the electronic
geometry of the water molecule is square planar instead of tetrahedral.
OBJ: Explain the factors responsible for the tetrahedral molecular geometry.
TOP: Valence Shell Electron Pair Repulsion (VSEPR) Theory | Valence Bond (VB) Theory

2. Explain why sulfur can share 10 or 12 electrons, yet oxygen, in the same group, cannot.
OBJ: Explain the origin of the exceptions to the octet rule.

TOP: Valence Bond (VB) Theory | Lewis Structures
3. Discuss how the Valence Bond theory explains why Be can make 2 and only 2 bonds.
OBJ: Explain how VBT limits the number of bonds in a molecule.

4. In terms of the geometry of the orbitals, explain why a quadruple bond is not possible.
OBJ: Describe the orbital atomic geometry required to form a quadruple bond.
TOP: Compounds Containing Double or Triple Bonds | Compounds Containing Triple Bonds |
Valence Bond (VB) Theory
5. Double bonds count as only one region of high electron density instead of two. Comment on how the
fact that CO2 is nonpolar confirms this.
OBJ: Explain why multiple bonds are treated as a single electron group in VSEPR
6. Consider a theoretical XeF6 molecule. What would you predict for hybridization of the orbitals? Can
you think of a possible geometry?
OBJ: Describe the central atom electronic and molecular geometry, and hybridization of theoretical
molecule.
TOP: Valence Shell Electron Pair Repulsion (VSEPR) Theory | Valence Bond (VB) Theory

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silicates of alumina), its organic matter (humus and organic nitrogen), its
content of carbon dioxid (carbonates of the alkaline earths), and the part of it
soluble in acids. A determination of these values gives the analyst a general view
of the type of soil with which he is engaged, and leads him to adopt such a
method of more extended analysis as the circumstances of the case may demand.
For this reason those operations which relate to the above determinations are
placed first in the processes to be performed, while the estimation of the more
particular ingredients of the soil is left for subsequent elaboration.
Next follows a description of the standard methods of estimating the more
important elements passing into solution on treatment of a soil sample with an
acid. The method of treating the insoluble residue, and the detection and
estimation of rare or unimportant soil constituents, closes the analytical study of
the soils.
With respect to the determination of nitrogen as nitric or nitrous acid in the
soil and drainage waters, it has been thought proper to collect all standard
methods relating particularly thereto into one group, and they will appear
separate from the methods under nitrogen analysis in fertilizers.
The question of the utility of chemical soil analyses is one which has been the
subject of vigorous discussion, a discussion which finds no proper place in a
work of this character. Unless, however, intelligent soil analysis be productive of
some good it would be a thankless task to collect and arrange the details of the
processes employed. An accurate determination of the constituents of a soil may
not enable the chemist to recommend a proper course of treatment, but it will
help in many ways to develop a rational soil diagnosis which will permit the
physician in charge of the case, who last of all is the farmer, to follow a rational
treatment which in the end will be productive of good.
The analyst will find in the methods given all that are approved by bodies of
official or affiliated chemists, or by individual experience, and among them some
method may be found which, it is hoped, will be suited, in the light of our
present knowledge, to each case which may arise.
292. Reaction of the Soil.—In soils rich in decaying vegetable matter the
excess of acid is often great enough to produce a distinct acid reaction.
On the contrary, in arid regions the accumulation of salts near the surface may
produce the opposite effect.
The reaction of the soil may be determined with a large number of indicators
among which, for convenience, sensitive litmus paper, both red and blue, stand
in the front rank. A sample of the soil, from fifteen to thirty grams, is mixed with
water to a paste and allowed to settle. The litmus paper is then dipped into the
supernatant liquid.
293. Determination of Water in Soil.—The following problems are
presented:
(a) The Determination of Water in Fresh Samples taken in situ.—The content
of water in this case varies with the date and amount of rain-fall, the capacity of
the soil for holding water, the temperature and degree of saturation of the
atmosphere, and many other conditions, all of which should be noted at the time
the samples are taken.
(b) The Determination of Water in Air-Dried Samples.—In this case the soil is
allowed to remain in thin layers, and exposed to the air until it ceases to lose
weight. The quantity of water left is dependent on the capacity of the soil to hold
hygroscopic water and to the temperature and degree of saturation of the air.
(c) The Determination of the Total Water by Ignition.—This process not only
gives the free and hygroscopic moisture, but also combined water present in the
hydrous silicates and otherwise. The estimation is complicated by the presence
of carbonates and organic matter.
294. Determination of Water in Fresh Samples.—This determination
requires that the sample, when taken in the field, should be so secured as to be
weighed before any loss of moisture can take place. For this purpose it can be
sealed up in tubes or bottles and preserved for examination in the laboratory.
According to Whitney, the relations of soils to moisture and heat are such
prominent factors in the distribution and development of agricultural crops, that
the determination of the actual moisture content of soils in the fields should be
considered a necessary part of the meteorological observations, and of far more
importance, indeed, or having far more meaning to the agriculturist than the
simple record of the rain-fall.
In order to determine the relation of the soil to moisture, uninfluenced by the
varying conditions of cultivation and of the different size of crop, he
recommends that a small plot of ground be reserved at each station, adjacent to
the soil thermometers, where the samples may be taken for the moisture
determinations. No crops should be allowed to grow on this area and the soil is
not to be disturbed, except that weeds and grass are carefully removed by hand
when necessary. Samples of the soil should be taken every morning at 8 o’clock,
by correspondents in the principal soil formations from the different parts of the
area under observation, and sent by mail to the laboratory.
The samples should be taken as described in paragraph 65. The locality and
date are written on a label attached to the tube. The tube contains about sixty or
seventy grams of soil, and the moisture determination is made on this in the
laboratory in the usual way.
It would be desirable to have this sample represent a depth of from six to nine
inches, thus rejecting the surface three inches which are more liable to sudden
and accidental changes. These tubes are very inexpensive, and a sufficient
number should be purchased to keep each station supplied. The sample
represents a definite depth, and it does not have to be subsampled or even
transferred in the field. This record of the moisture of the soil will show the
amount of moisture which the different soils can maintain at the disposal of the
plants, which, together with the temperature of the soil, is believed to be a most
important factor in crop distribution and development.
295. Method of Berthelot and André.—The estimation of the water
according to Berthelot and André[189] should be made under three forms; viz.,
1. Water eliminated spontaneously at ordinary temperatures.
2. Water eliminated by drying to constant weight at 110°.
3. Water eliminated at a red heat.
The water may be determined directly on a sample weighed at the time of
taking and afterwards dried in the open air, and finally, if necessary, in a
desiccator. For a general idea the desiccation should be made on a sample of 100
grams, for exact work on ten grams. The dish in which the drying takes place
should be shallow, and during the time the sample should be frequently stirred
and thoroughly pulverized with a spatula which is weighed with the dish. The
drying in the air should continue several days. The data obtained are not fixed
since they depend on the temperature and the degree of saturation of the air
with aqueous vapor. The variations due to these causes, however, are not very
wide. The process may be regarded as practically finished when successive
weights sensibly constant are obtained. In this state the soils contain very little
water eliminable at 110°.
296. Estimation of Water Remaining after Air-Drying.—The sifted
sample is placed in quantities of five or ten grams in a flat-bottomed dish and
dried at 110° to constant weight. This treatment not only removes the moisture,
but all matters volatile at that temperature.
Petermann,[190] in the Agricultural Station, at Gembloux, practices drying the
sample to constant weight at 150°.
It is further recommended by Petermann to determine total volatile and
combustible matters by igniting to incipient redness, allowing to cool,
moistening with distilled water, and drying at 150°.
The German experiment stations[3] estimate hygroscopic moisture for
analytical calculations by drying to constant weight at 100°. In determining loss
on ignition, however, the preliminary drying is made at 140°, with the exception
of peaty samples where so high a temperature is not admissible.
The Official Agricultural Chemists[191] place five grams of air-dried soil in a
flat-bottomed and tared platinum dish; heat in an air-bath to 110° for eight
hours; cool in a desiccator, and weigh; repeat the heating, cooling, and weighing,
at intervals of an hour till constant weight is found, and estimate the hygroscopic
moisture by the loss of weight. Weigh rapidly to avoid absorption of moisture
from the air.
In the German laboratories, according to König,[192] from ten to twenty grams
of the fine earth, properly prepared by air-drying and sifting, for analysis, are
heated at 100° to constant weight. For control, five grams are placed in a
desiccator over sulfuric acid for two or three days.
Wolff directs that a small portion of the well-mixed earth, for example, twenty
grams, be spread out on a flat zinc plate, and its changes in weight observed
through several days. These observations are continued until the variations are
so slight that the means can be determined with sufficient exactness from the
last weighings. The soil is then dried at 125° in a hot air-chamber. The loss in
weight will give the mean hygroscopic moisture in the soil under the conditions
in which the experiment is made.
297. Drying in a Desiccator.—The sample dried as indicated previously by
the method of Berthelot and André is placed in a desiccator over sulfuric acid. It
is better to have the sample traversed by a current of perfectly dry air, and in this
case it should be placed in a tube, which is closed while weighing, to prevent
absorption of moisture. Much time is also required for this operation, and it does
not possess the practical value of the method of drying in the free air.
298. Water Set Free at 110°.—This is determined by Berthelot and André
on a weight of five to ten grams of soil. The sample which has been employed for
the preceding determination may be used. While this is going on in an air-bath
heated to 110°, about ten times as much soil should be dried for the same time at
the same temperature, and this should be preserved in a well-stoppered flask. All
subsequent determinations are to be made with the soil dried at 110°.
The loss of weight in a soil increases with the temperature to which it is
exposed. The apparent quantity of water, therefore, determined at 140° or 180°
is always greater than that obtained at 110°. But when the temperature exceeds
110° there is danger of decomposing organic bodies with the loss of a part of
their constituent elements. Carbon dioxid and ammonia may also be lost, as well
as acetic acid and other volatile bodies.
299. Loss on Ignition.—The loss on ignition represents any hygroscopic
moisture not removed by previous drying, all water in combination with mineral
matters as water of constitution, all organic acids and ammoniacal compounds,
all organic matter when the ignition is continued until the carbon is burned
away, all or nearly all of the carbon dioxid present in carbonates, and, finally,
some of the chlorids of the alkalies, if the temperature have been carried too
high or been continued too long.
The loss of carbon dioxid in carbonates may be mostly restored by moistening
the ignited mass two or three times with ammonium carbonate, followed by
gentle ignition for a few minutes to incipient redness, to remove excess of the
reagent. The apportionment of the rest of the loss justly among the remaining
volatile constituents of the original sample is a matter of some difficulty but may
be approximately effected by the methods to be submitted.
300. Determination of Loss on Ignition.—Method of the Official
Agricultural Chemists. The platinum crucible and five grams of soil used to
determine the hygroscopic moisture may be employed to determine the volatile
matter. Heat the crucible and dry soil to low redness. The heating should be
prolonged till all organic material is burned away, but below the temperature at
which alkaline chlorids volatilize. Moisten the cold mass with a few drops of a
saturated solution of ammonium carbonate, dry, and heat to 150° to expel excess
of ammonia. The loss in weight of the sample represents organic matter, water of
combination, salts of ammonia, etc.
According to Knop[193] the total loss on ignition is determined as follows:
About two grams of the fine earth are carefully ignited until all organic matter is
consumed. The sample is then mixed with an equal volume of finely powdered,
pure oxalic acid, and again heated until all the oxalic acid is decomposed. After
cooling, the sample is weighed, again mixed with oxalic acid, ignited, cooled,
weighed, and the process continued until the weight is constant.
The method recommended by König consists in igniting about ten grams of
the fine earth at the lowest possible temperature until all the humus is
destroyed. Thereafter the sample is repeatedly moistened with a solution of
ammonium carbonate and ignited after drying at 100°, until constant weight is
obtained. In soils rich in carbonates some carbon dioxid may be lost by the
above process. For this a proper correction can be made by estimating the
carbon dioxid in the sample, both before and after the execution of the above
described process.
The method described by Frühling as much used in the German laboratories,
consists in igniting ten grams of the fine earth, previously dried at 140° in a
crucible placed obliquely on its support and with the cover so adjusted over its
mouth as to give a draft within the body of the crucible. The ignition, at a gentle
heat is continued until on stirring with a platinum wire no evidence of
unconsumed carbon is found. The moistening with solution of ammonium
carbonate, should not take place until the contents of the crucible are cool.
Subsequent ignition, at a low heat for a short time, will remove the excess of
ammonium salt.
301. Method of Berthelot and André.[194]—The earth dried at 110°
contains still a greater or less quantity of combined water. This is the water
united with alumina, silica and certain salts, but not the water of constitution
belonging to organic bodies. The exact estimation of this water offers many
difficulties. The determination of loss obtained at a red heat embraces:
(1) The water combined with zeolitic silicates, with alumina and with organic
compounds.
(2) The water produced by the combustion of the organic compounds.
(3) The carbon dioxid resulting from the partial decomposition of the calcium
and magnesium carbonates.
(4) The carbon burned and the nitrogen lost during ignition. The measure of
the loss of weight in an earth heated to redness in contact with the air is not
therefore, an exact process of estimating water or even volatile matters.
A better defined result is obtained in carefully burning a known weight of
earth either in a current of free oxygen, or with lead chromate. The water
produced in such a combustion is secured in a ᥩ tube filled with pumice stone
saturated with sulfuric acid, the carbon dioxid being absorbed afterwards in
potash bulbs and by solid potash. The weight of earth burned is chosen so as to
furnish a convenient weight of both water and carbon dioxid. In general about
five grams are sufficient. When the combustion is made with oxygen, the soil is
contained in a boat and the products of the combustion are carried over a long
column of copper oxid heated to redness. The residue left in the boat is weighed
at the end of the operation, and in this residue it is advisable to determine any
undecomposed carbonate. Should the sample burn badly and be mixed with
carbonaceous matter at the end of the operation, it will be necessary to
substitute the lead chromate method. In this case, of course, the residue left after
combustion is not weighed. Whichever method is employed gives a quantity of
water originally combined with the soil, plus the quantity arising from the
combustion of the hydrogen of the organic matter. The details of the processes
for organic combustion, will be given in a subsequent part of this manual. It is
not possible to divide the water between these two sources directly, but this can
be done by calculation, which gives results lying within the limits of probability.
The method follows:
The organic nitrogen, determined separately, by soda-lime, the method of
Kjeldahl, or volumetrically, is derived from proteid principles resembling
albuminoids containing about one-sixteenth of their weight of nitrogen. The
nitrates contained in the earth are in such feeble proportion, as to be negligible
in this calculation. The total weight of these nitrogenous principles in the soil is
therefore easily calculated. The carbon contained in the proteids is then
calculated on a basis of 53 per cent of their total weight, and the hydrogen on a
basis of 7.2 per cent. From the weight of the total organic carbon (determined as
described further on) is subtracted the carbon present in the proteids. The
remainder corresponds to the organic carbon present as carbohydrates,
(ligneous principles) containing 44.4 per cent carbon and 6.2 per cent hydrogen.
By adding together the weight of the hydrogen contained in the ligneous
principles, and the hydrogen contained in the proteids, and multiplying the sum
by 9, the weight of water formed by the combustion of all the organic matter in
the sample is obtained. This is subtracted from the weight of the total water
obtained by direct determination as described above. The difference represents
the weight of water combined with the silicates, etc., as well as with organic
matters.
302. Method of Von Bemmelén.[195]—According to the view of Von
Bemmelén, the soil contains colloidal humus and colloidal silicate, which
complicate the determination of water. The colloids retain water in varying
quantities, depending upon the following conditions:
(1) Upon their composition and state of molecular equilibrium.
(2) Upon the pressure of the aqueous vapor of the room.
(3) Upon the temperature.
At each degree of temperature, the quantity of absorbed water which a colloid
can retain in a room saturated with aqueous vapor, is different. The quantity of
water which air-dried earth gives off at 100°, has therefore, no special
significance unless all conditions are known.
In addition to the estimation of the quantity of water which soils, in their
natural condition, are capable of taking up and holding, at ordinary
temperatures, the estimation of the quantity of water which they can take up in
different temperatures in rooms saturated with aqueous vapor should be of
interest. It follows, therefore, that there is no special value in data obtained by
drying earth at 100° or 110°. For the purpose of comparison, he prefers to select
that point at which the soil is dried over sulfuric acid, the point at which the
tension of the water vapor in the earth, at a temperature of plus or minus 15°,
approaches zero. The water which still remains in the earth under these
conditions is characterized as firmly combined water.
Von Bemmelén truly observes that only in soils which contain no carbonates
and no chlorids and sulfids, can the loss on ignition be regarded as the sum of
the humus and water content. By moistening with ammonium carbonate, the
correction for lime or carbon dioxid cannot be correctly made as has been the
custom up to the present time. In the first place, ignited magnesia, when it has
lost its carbon dioxid, does not take this up completely on moistening with
ammonium carbonate; in the second place, reactions with the chlorids may take
place; and in the third place, the lime which is in the humus will be converted
into calcium carbonate. Chlorids on ignition may be volatilized or oxidized. The
sulfuric acid formed from the sulfids, on ignition, can expel carbon dioxid;
further than this the iron of pyrites takes up oxygen on ignition. All these
influences make the numbers obtained from loss on ignition extremely variable.
With sea soils, Von Bemmelén has weighed the soil after the elementary
analysis and estimated, in addition to the carbon dioxid, both chlorin and
sulfuric acid therein. The comparison of these estimations with those of CO₂, Cl,
SO₃ and S, made in the original soil, gave the necessary corrections; viz., for the
increase in the weight through oxidation of sulfur and iron, and for the decrease
in weight through the volatilization of sodium chlorid, sulfur, and carbon dioxid.
A trace of chlorin was evolved as ferric chlorid, nevertheless, the molecular
weight of sodium chlorid, 58.5, is scarcely different from the equivalent quantity
of ferric chlorid 54.1. For this reason the estimation of loss of water, on ignition,
of sea soils is less exact than that of soils which are free from carbonates and
sulfids and which, as is usually the case with tillable soils, contain only small
quantities of chlorids and sulfates.
The Strongly Combined Water.—Water which, at a temperature of plus or
minus 15°, in a dry room, still remains in the soil, is chiefly combined according
to Von Bemmelén with the colloidal bodies therein. Its estimation, presents,
naturally, difficulties and is not capable of any great exactness. The quantity of
strongly combined water, on the one hand is determined from the difference
between the loss on ignition and the quantity of humus present, calculated from
the content of carbon; on the other hand, from the difference between the water
obtained by elementary analysis and the water which corresponds to the
calculated quantity of humus. If the hydrogen content of humus is correctly
taken and no appreciable error is introduced through the factor 1.724, both of
these differences must agree. On the other hand the hydrogen content of the
humus can be computed from the difference between the water found and the
calculated content of the firmly combined water.
The hydrogen content of humus bodies, dried at 100°, varies between four and
five per cent. Eggertz has found the content from 4.3 to 6.6 per cent of hydrogen
in thirteen soils which he first treated with dilute hydrochloric acid then
extracted with ammonia or potash lye and precipitated this alkaline extract with
acid. The method of applying these principles to soil analysis is indicated in the
following scheme:
A volcanic earth from Deli gave, on elementary analysis:
Per cent.
Carbon 2.94
Water 14.78
Nitrogen 0.28
Loss on ignition 17.54
First Calculation.
Per cent.
Loss on ignition 17.54
Humus = carbon, 2.94 × 1.724 = 5.07
Difference = firmly combined water 12.47
Assuming that a humus dried over sulfuric acid contains five per cent of
hydrogen, the second calculation is made as follows.
Second Calculation.
5.00 humus × 5 per cent = 0.25 per cent of hydrogen in humus corresponding to 2.28 per
cent of water.
Per cent.
Water found 14.79
Difference = firmly combined water 12.51
Third Calculation.
Per cent.
Firmly combined water 12.47
Water from the hydrogen in humus 2.28
Total water 14.75
Found 14.79
In this way, in three other volcanic earths and in an ordinary alluvial clay from
Rembang, there were found by analysis and by calculation the following
percentages of water:
1. 2. 3. 4. 5.
Percentage of water calculated 14.75 7.74 8.06 4.90 6.01
„„„ found 14.97 7.63 8.05 4.70 6.00
On the contrary, when the calculation is made from sea-slime taken from
under the water a higher content of hydrogen must be assumed; viz., about six
per cent. In two samples of sea-slime calculated in this way the following
numbers were obtained:
Percentage of water calculated 8.61 3.71

„„„ found 8.53 3.57
It is, therefore, quite evident that the organic compounds of soil taken from
under the sea-water are richer in hydrogen than those exposed to the air or in
cultivation.
303. General Conclusions.—In the foregoing paragraphs have been
collected the most widely practiced methods of determining moisture in soil in
both a free and combined state. The following conclusions may serve to guide
the analyst who endeavors to determine the water in any or all of its conditions:
(1) In determining water in fresh samples the method of Whitney is
satisfactory. Although the samples taken by this method are small they may be
easily secured in great numbers over widely scattered areas, and can be easily
transported without change. These samples should be dried at 100° to 110° for
rapid work, or where time can be spared may be air-dried.
(2) For a simple determination of the water left in the soil after air-drying
(hygroscopic water) the method of the Association of Official Agricultural
Chemists may be followed. There is much difference of opinion in respect of the
proper temperature at which this moisture is to be determined. Much here
depends on the nature of the soil. An almost purely mineral soil may safely be
dried at 140° or 150°. A peaty soil, on the contrary, should not be exposed to a
temperature above 100°. For general purposes the temperature chosen by the
official chemists is to be recommended.
(3) Water of composition can only be determined by ignition. As has been fully
shown, this process not only eliminates the water, but also destroys organic
matter, decomposes carbonates and sulfids, and, to some extent, chlorids.
Subsequent repeated treatment with ammonium carbonate may restore the loss
due to carbon dioxid, but in many cases not entirely. The water which comes
from organic matter may be approximately calculated from the humus content
of the sample, but as will be seen further on the methods of estimating humus
itself are only approximate. Nevertheless, in distributing the losses on ignition
properly to the several compounds of the soil there is no better method now
known than that of taking into consideration the humus content and carbonates
present. The principles of procedure established by Berthelot and André, and
Von Bemmelén, are to be applied in all such cases, modified as circumstances
may arise according to the judgment of the analyst.
304. Estimation of the Organic Matter of the Soil.—The organic matter
in the soil may be divided into two classes. First, the undecayed roots and other
remains of plant and animal life, and the living organisms existing in the soil.
The study of the organisms which are active in the condition of plant growth will
be the subject of a special chapter. Second, the decayed or partially decayed
remnants of organic matter in the soil known as humus. Such matter may be
present in only minute traces, as in barren sand soils, or it may form the great
mass of the soil under examination, as in the case of peat, muck, and vegetable
mold. It is with the investigation of the second class of matter that the analyst
has chiefly to do at present. The problems which are to be elucidated by the
analytical study of such bodies are the following: (1) The total quantity of such
matter in the soil. (2) The determination of the organic carbon and hydrogen
therein. (3) The determination of total nitrogen. (4) The determination of the
availability of the nitrogen for plant growth. (5) The estimation of the humic
bodies (humus, humic acid, ulmic acid, etc.).
The importance of humus in the promotion of plant growth is sufficient excuse
for the somewhat extended study of the principles which underlie the analytical
methods, and the methods themselves, which follow.
305. Total Quantity of Organic Matter.—The total approximate quantity
of organic matter in the soil can be determined by simple ignition, in the manner
noted in paragraphs 294 and 295. The proper correction for free and combined
water being applied by the further copper oxid or lead chromate combustion of
the sample, and for carbonates and volatile chlorids, the approximate total of the
organic matter of all kinds is obtained.
306. Estimation of the Organic Carbon.—To estimate the organic
carbon in an earth the sample may be burned in a current of oxygen, or after
mixing with lead chromate.
In a Current of Oxygen.—When burned in a current of oxygen the sample is
held in a boat and the gases arising from the combustion directed over copper
oxid at a red heat. The carbon thus disappears as carbon dioxid and is absorbed
and weighed in the usual way.
With Lead Chromate.—The lead chromate employed should be previously
tested since it often contains other compounds, especially lead acetate and
nitrate, furnishing in the one case both carbon dioxid and water, and in the other
hyponitric acid.
From two to ten grams of earth are employed, according to its richness in
organic matter. The total carbon dioxid is obtained in this process both from
carbonates and organic bodies. The water and carbon dioxid are secured and
weighed in the usual manner.
The oxygen method should be used in all cases possible. Although it does not
always give the whole of the carbon dioxid present as carbonates, the rest can be
easily estimated by treating the residue in the boat with hydrochloric acid, in an
apparatus for estimating that gas.
Calculation of Results.—The whole of the carbon dioxid is determined either
by direct combustion with lead chromate, or by taking the sum of the amounts
by burning in a stream of oxygen and treating the residue in a carbon dioxid
apparatus.
The carbon dioxid contained in the original carbonates should be determined
by direct treatment of the sample in the usual way.
The carbon in organic compounds is determined by subtracting the carbon
present as carbonates from the total.
From the organic carbon contained in the soil the humus is calculated by
Wolff on the supposition that it contains fifty-eight per cent of carbon. It is,
therefore, only necessary to multiply the percentage of carbon found by 1.724, or
the carbon dioxid found by 0.471, to determine the quantity of humus in the
dried soil.
307. Details of the Direct Estimation of Carbon in Soils by Various
Methods.—(1) Oxidation by Chromic Acid.—The method of Wolff by oxidation
with chromic acid has been worked out in detail by Warington and Peake.[196] It
consists in treating the soil with sulfuric acid and potassium bichromate, or by
preference with a mixture of sulfuric and chromic acids, the carbon dioxid
evolved being estimated in the usual way. This method is recommended by
Fresenius as an alternative to a combustion of the soil with copper oxid or lead
chromate. It is apparently the method which has been most generally employed
in agricultural investigations.
Ten grams of the finely powdered soil are placed in a flask of about 250 cubic
centimeters capacity, provided with a caoutchouc stopper, through which pass
two tubes, one for the supply of liquids, the other for the delivery of gas. The soil
is treated with twenty cubic centimeters of water and thirty cubic centimeters of
oil of vitriol; and the whole, after being thoroughly mixed, is heated for a short
time in a water-bath, the object in view being the decomposition of any
carbonates existing in the soil. Air is next drawn through the flask to remove any
carbon dioxid which has been evolved. The stopper is next removed, and
coarsely powdered potassium bichromate introduced. In the case of a soil
containing three per cent of carbon, six grams of bichromate will be found
sufficient, a portion remaining undissolved at the end of the experiment. The
stopper is then replaced, its supply-tube closed by a clamp, and the delivery-tube
connected with a series of absorbents contained in ᥩ tubes. The first of these
tubes contains solid calcium chlorid; the second, fragments of glass moistened
with oil of vitriol; the third and fourth are nearly filled with soda-lime, a little
calcium chlorid being placed on the top of the soda-lime at each extremity. The
last named tubes are for the absorption of carbon dioxid, and have been
previously weighed. The series is closed by a guard-tube containing soda-lime,
with calcium chlorid at the two ends.
The flask containing the soil and bichromate is now gradually heated in a
water-bath, the contents of the flask being from time to time mixed by agitation.
A brisk reaction occurs, carbon dioxid being evolved in proportion as the soil is
rich in organic matter. The temperature of the water-bath is slowly raised to
boiling as the action becomes weaker, and is maintained at that point till all
action ceases. As bubbles of gas are slowly evolved for some time, it has been
usual in these experiments to prolong the digestion for four or five hours. When
the operation is concluded the source of heat is removed, an aspirator is
attached to the guard-tube at the end of the absorbent vessels, and air freed from
carbon dioxid is drawn through the flask and through the whole series of ᥩ
tubes. The ᥩ tubes filled with soda-lime are finally weighed, the increase in
weight showing the amount of carbon dioxid produced. The object of the calcium
chlorid placed on the surface of the soda-lime is to retain the water which is
freely given up when the soda-lime absorbs carbon dioxid. The second ᥩ tube
filled with soda-lime does not gain in weight till the first is nearly saturated; it
thus serves to indicate when the first tube requires refilling. The same tubes may
be used several times in succession.
No increase in the carbon dioxid evolved is obtained by substituting chromic
acid for potassium bichromate.
The organic matter of the soil appears to the eye to be completely destroyed by
the digestion with sulfuric acid and potassium bichromate; the residue of soil
remaining in the flask when washed with water is perfectly white, or the dark
particles, if any, are found to be unaltered by ignition, and therefore to be
inorganic in their nature. Under these circumstances considerable confidence
has naturally been felt in this method. The complete destruction of the humic
matter of the soil does not, however, necessarily imply that the carbon has been
entirely converted into carbon dioxid as has been pointed out by Wanklyn.
According to his demonstration of the action of chromic acid on organic matter
the oxidation frequently stops short of the production of carbon dioxid. While
oxidation with chromic acid apparently leads to a complete reaction when the
carbon is in the form of graphite, it would probably yield other products than
carbon dioxid when the carbon exists as a carbohydrate. The doubt thus raised
as to the correctness of the results yielded by the chromate method makes it
desirable to check the work by the use of other methods for the determination of
carbon. For this purpose Warington and Peake recommend:
(2) Oxidation with Potassium Permanganate.—In the trials with this method
ten grams of soil are digested in a closed flask with a measured quantity of
solution of caustic potash containing five grams of potash for each twenty cubic
centimeters, and crystals of potassium permanganate. Seven grams of the
permanganate are found to be sufficient for a soil containing 3.3 per cent of
carbon. The flask is heated for half an hour in boiling water, and then for one
hour in a salt-bath. The flask during this digestion is connected with a small
receiver containing a little potash solution, to preserve an atmosphere free from
carbon dioxid; distillation to a limited extent is allowed during the digestion in
the salt-bath.
The first part of the operation being completed a rubber stopper, carrying a
delivery and supply-tube, is fitted to the flask, which is then connected with the
system of ᥩ tubes already described. Dilute sulfuric acid is then poured down
the supply-tube, a water-bath surrounding the flask is brought to boiling, and
maintained thus for one hour, after which air, free from carbon dioxid, is drawn
through the apparatus, the ᥩ tubes containing soda-lime being finally
disconnected and weighed.
In the first stage of this method the carbon of the organic matter is converted
into carbonate, and probably also into potassium oxalate.[197] In the second stage
the oxalate is decomposed by the sulfuric acid and permanganate, and the
carbon existing, both as oxalate and carbonate, is evolved as carbon dioxid, and
absorbed by the weighed soda-lime tubes. Both F. Schulze and Wanklyn have
employed potassium permanganate for the determination of organic carbon, but
they have preferred to calculate the amount of carbon from the quantity of
permanganate consumed, as, however, by so doing everything oxidizable by
permanganate is reckoned as carbon, it seems better to make a direct
determination of the carbon dioxid formed.
From the amount of carbon dioxid found, is to be subtracted that existing as
carbonates in the soil, and in the solution of potash used. For this purpose an
experiment is made with the same quantities of soil and potash previously
employed, but without permanganate, and the carbon dioxid obtained is
deducted from that yielded in the experiment with permanganate. If the potash
used contains organic matter two blank experiments will be necessary, one with
potash and permanganate, and one with soil alone.
A further difficulty arises from the presence of chlorids in the materials, which
occasions an evolution of free chlorin when the permanganate solution is heated
with sulfuric acid. This error occurs also with the chromic acid method, but in
that case the quantity of chlorid is merely that contained in the soil, which is
usually very small; in the permanganate method we have also the chlorid present
in the caustic potash, and this is often considerable. Corrections for chlorin by
blank experiments are unsatisfactory, the amount of chlorin which reaches the
soda-lime tubes depending in part on the degree to which the calcium chlorid
tube has become saturated with chlorin. It is better therefore to remove the
chlorin in every experiment by the plan which Perkin has suggested, by inserting
a tube containing silver foil, maintained at a low red heat, between the flask and
the absorbent ᥩ tubes.
The amount of carbon dioxid yielded by oxidation with potassium
permanganate is found to be considerably in excess of that obtained by oxidation
with chromic acid; to ascertain whether these higher results really represented
the whole of the carbon present in the soil, trials were next made by actual
combustion of the soil in oxygen.
(3) Combustion in Oxygen.—The most convenient mode of carrying out the
combustion of soil is to place the soil in a platinum boat, and ignite it in a
current of oxygen in a combustion tube partly filled with cupric oxid. A wide
combustion tube is employed, about twenty inches long, and drawn out at one
end; the front of the tube is filled for eight inches with coarse cupric oxid, the
hind part is left empty to receive the platinum boat. The drawn out end of the
combustion tube is connected with a series of absorbent ᥩ tubes, quite similar to
those employed for the estimation of carbon dioxid in the chromic acid method.
Between these absorbent vessels and the combustion tube is placed a three-
bulbed Geissler tube filled with oil of vitriol. The oil of vitriol is quite effective in
retaining nitrous fumes. The wide end of the combustion tube is connected with
a gas-holder of oxygen; the oxygen gas is made to pass through a ᥩ tube of soda-
lime before entering the combustion tube, to remove any possible contamination
of carbon dioxid.
In starting a combustion the part of the combustion tube containing the cupric
oxid is brought to a red heat, and oxygen is passed for some time through the
apparatus. Ten grams of soil, previously dried, are placed in a large platinum
boat, which is next introduced at the wide end of the combustion tube. The
combustion is conducted in the usual manner, a current of oxygen being
maintained throughout the whole operation. It is very useful to terminate the
whole series of absorbent vessels with a glass tube dipping into water; the rate at
which the gas is seen to bubble, serves as a guide to the supply of oxygen from
the gas-holder, the consumption of oxygen varying, of course, with different
soils, and at different stages of the combustion. At the close of the combustion,
oxygen, or air freed from carbon dioxid, is passed for some time through the
apparatus to drive all carbon dioxid into the absorbent vessels. One experiment
can be followed by another as soon as the hind part of the combustion tube has
cooled sufficiently to admit a second platinum boat. The same combustion tube
can be employed for several days, if packed in the usual manner in asbestos.
The presence of carbonates in the soil occasions some difficulty in working the
combustion method, as a part of this carbon dioxid will, of course, be given up
on ignition, and be reckoned as carbon. The simplest mode of meeting this
difficulty is to expel the carbon dioxid belonging to the carbonates before the
combustion commences. The method of Manning; namely, treatment with a
strong solution of sulfurous acid, may be employed for this purpose. The ten
grams of soil taken for combustion are placed in a flat-bottomed basin, covered
with a thin layer of sulfurous acid, and frequently stirred. After a time the action
is assisted by a gentle heat. When the carbonates have been completely
decomposed the contents of the basin are evaporated to dryness on a water-
bath; the dry mass is then pulverized, and removed to the platinum boat for
combustion in oxygen. For the action of the sulfurous acid to be complete it is
essential that the carbonates should be in very fine powder, since even chalk is
but imperfectly attacked when present in coarse particles.
308. Comparison of Methods.—A considerable number of soils analyzed
by the chromic acid method and by the combustion, method, by Warington and
Peake, with the assistance of Cathcart, shows the following comparisons:
Percentage of Carbon Found by Two Methods in Soils Dried at 100°.
Chromic acid Combustion

method. method.
No. Kind of Exp. Exp. Mean. Exp. Exp. Mean. Per cent. yielded by
soil. 1. 2. 1. 2. chromic acid.
1. Old 2.85 2.79 2.82 3.58 3.55 3.57 79.0
pasture
2. „„ 2.83 2.79 2.81 3.57 3.53 3.55 79.1
3. „„ 2.76 2.76 2.76 3.46 3.46 3.46 79.7
4. „„ 2.74 2.76 2.75 3.37 3.38 3.38 81.4
5. „„ 2.64 2.54 2.59 3.31 3.36 3.34 77.5
6. „„ 2.51 2.43 2.47 3.15 3.15 3.15 78.4
7. „„ 2.40 2.44 2.42 3.09 3.13 3.11 77.8
8. New 1.92 1.93 1.93 2.41 2.40 2.41 80.1
pasture
9. „„ 1.66 1.81 1.74 2.39 2.43 2.41 72.2
10. Arable 1.78 1.78 1.78 2.14 2.13 2.14 83.2
soil
11. „„ 1.21 1.14 1.18 1.40 1.43 1.42 83.1
12. Subsoil 0.28 0.27 0.28 0.37 0.38 0.38 73.7
Of the above soils the arable soils, Nos. 10 and 11, were the only ones
containing carbonates in any quantity exceeding a minute trace. The two soils in
question were treated with sulfurous acid before combustion, the others not.
All the determinations by the chromic acid method were made by Mr. P. H.
Cathcart, with the exception of Nos. 9 and 12, which were executed by another
experimenter, and are seen to give distinctly lower results. Excluding these two
analyses the relation of the carbon found by the two methods is tolerably
constant, the average being 79.9 of carbon found by oxidation with chromic acid
for 100 yielded by combustion in oxygen. The results obtained by the chromic
acid method thus appear to be very considerably below the truth.
Four typical soils were analyzed by the permanganate, as well as by the
chromic acid and combustion methods. The results obtained were as follows:
Percentage of Carbon Found by Three Methods in Soils Dried at 100°.
Permanganate
method.
Kind of Chromic Yielded by
soil. Combustion acid Exp. Exp. permanganate if
method. method. 1. 2. Mean. carbon by
Mean. Per Mean. Per Per Per Per combustion =
cent. cent. cent. cent. cent. 100. Per cent.
Old
pasture 3.55 2.81 3.26 3.30 3.28 92.4
New
pasture 2.41 1.93 2.29 2.30 2.30 95.4
Arable
soil 1.42 1.18 1.28 1.33 1.31 92.3
Subsoil 0.38 0.28 0.34 0.34 0.34 89.5
Oxidation by permanganate thus gives a much higher result than oxidation

with chromic acid; but even the permanganate fails to convert the whole of the
carbon into carbon dioxid, the product with permanganate being on an average
of the four soils 92.4 per cent of that yielded by combustion in oxygen.
Wanklyn states that a temperature of 160°–180° is necessary in some cases to
effect complete oxidation with permanganate and caustic potash. Such a
temperature is found impracticable when dealing with soil, from the action of
the potash on the silicates present; hence possibly the low results obtained.
Combustion in oxygen appears from these experiments to be the most
satisfactory method for determining carbon in soil, nor is this method, on the
whole, longer or more troublesome than the other methods investigated.
Warington and Peake have further determined the loss on ignition of the four
soils mentioned above, with the view of comparing this loss with the amount of
organic matter calculated from the carbon actually present. In making this
calculation they have taken as the amount of carbon in the soil, that found by
combustion in oxygen, and have assumed with Schulze, Wolff, and Fresenius,
that fifty-eight per cent of carbon will be present in the organic matter of soils.
The four soils were heated successively at 100°, 120°, and 150°, till they ceased
to lose weight; the loss on ignition in each of these stages of dryness is shown in
the following table:
Percentage Loss on Ignition Compared with Organic Matter Calculated
from Carbon.
Between Between Between

100° and 120° and 150° and Organic matter at fifty-
ignition. ignition. ignition. eight per cent carbon.
Kind of
soil. Per cent. Per cent. Per cent. Per cent.
Old
pasture 9.27 9.06 8.50 6.12
New
pasture 7.07 6.88 6.55 4.16
Arable
soil 5.95 5.70 5.61 2.44
Clay
subsoil 5.82 5.39 4.76 0.65
The loss on ignition is seen to be in all cases very considerably in excess of the
organic matter calculated from the carbon, even when the soil has been dried at
as high a temperature as 150°. The error of the ignition method is least in soils
rich in organic matter, as, for instance, the old pasture soil in the above table.
The error reaches its maximum in the case of the clay subsoil, which contains
very little carbonaceous matter, but is naturally rich in hydrated silicates, which
part with their water only at a very high temperature.
The above methods of Warington and Peake have been given in detail, and in
almost the verbiage of the authors for the reason that the working directions are
clearly set forth, and may serve, therefore, as guides to the previous methods
where only general indications of manipulation have been given.
309. Estimation of Organic Hydrogen.—The estimation of the total
hydrogen is made without difficulty either by burning the sample in a current of
oxygen or with lead chromate, and weighing the water produced. This water
comes from two sources, the pre-existing water and organic hydrogen. There is
no direct method of distinguishing one from the other. They may, however, be
estimated indirectly. The method of calculating the organic hydrogen has
already been given (paragraph 299). Experience shows that the hydrogen thus
calculated is a little greater than is necessary to form water with the whole of the
oxygen found in the organic matters.
310. Estimation of Organic Oxygen.—The determination of this oxygen
cannot be made directly. It is obtained by calculation, according to Berthelot and
André,[198] from the oxygen in the proteid and ligneous matters.
Let p represent the weight of the proteid bodies in a sample of soil.
Then O = p ×100
33.5
Let p′ = weight of ligneous bodies.

Then O′ = p′ ×100
49.4
The total oxygen = O + O′.

An approximate result is thus obtained, very useful to have when account is
taken of the oxidizing processes which go on in the soil during agricultural
operations.
311. Estimation of Humus (Matière Noire).—The original method of
determining this substance is due to Grandeau.[199] It is carried on as follows:
Ten grams of the fine earth are mixed with coarse sand previously washed with
acids and ignited. The mixture is placed in a small funnel, the bottom of which is
filled with fragments of glass or porcelain. The mass is moistened with ammonia
diluted with an equal volume of distilled water, and allowed to digest for three or
four hours. The ammonia dissolves the dark matter without attacking the silica.
The ammoniacal solution is displaced by treating the mass with pure water, or
water to which some ammonia has been added, and the whole of the dark matter
is thus obtained in a volume of twenty to fifty cubic centimeters of filtrate. The
filtrate is evaporated to dryness in a weighed platinum dish, and the weight of
residue is determined and the percentage of matière noire calculated therefrom.
The residue is incinerated, and when in sufficient quantity the phosphoric acid is
determined in the ash. In soils poor in humus a larger quantity than ten grams
may be taken. If the soil be previously treated with hydrochloric acid, Grandeau
recommends that the phosphoric acid be determined always in the ash of the
dark matter.
The method has undergone various modifications and, as given by Hilgard, is
now practiced as follows:
About ten grams of soil are weighed into a prepared filter. The soil should be
covered with a piece of paper (a filter) so as to prevent it from packing when
solvents are poured on it. It is now treated with hydrochloric acid from five-
tenths per cent to one per cent strong (twenty-five and one-third cubic
centimeters of strong acid and 808 cubic centimeters of water) to dissolve the
lime and magnesia which prevent the humus from dissolving in the ammonia.
Treat with the acid until there is no reaction for lime; then wash out the acid
with water to neutral reaction. Dissolve the humus with weak ammonia water,
prepared by diluting common saturated ammonia water (178 cubic centimeters
of ammonia to 422 cubic centimeters of water). Evaporate the humus solution to
dryness in a weighed platinum dish at 100°; weigh, then ignite; the loss of weight
gives the weight of humus.
The residue from ignition is carbonated with carbon dioxid, heated and
weighed, thus giving the ash. It is then moistened with nitric acid and
evaporated to dryness. The residue is treated with nitric acid and water, allowed
to stand a few hours, and the solution filtered from the insoluble residue, which
is ignited and weighed, giving the silica.
The soluble phosphoric acid is determined in the solution by the usual
method, as magnesium pyrophosphate. It usually amounts to a fraction, varying
from one-half to as little as one-tenth of the total in the soil. While the
phosphoric acid so determined is manifestly more soluble and more available to
vegetation than the rest of that found by extraction with stronger acid, it is
clearly not as available as that which, when introduced in the form of
superphosphates, exerts such striking effects even though forming a much
smaller percentage of the whole soil. Nevertheless, very striking agreement with
actual practice is often found in making this determination.
The estimation of humus by combustion, in any form, of the total organic
matter in the soil, gives results varying according to the season, and having no
direct relation to the active humus of the soil. The same objection lies against
extraction with strong caustic lye.
312. Modification of Grandeau’s Method for Determining Humus in
Soils.—According to Huston and McBride[200] the function of the vegetable
matter in the soil has long been a matter of contention among those interested in
the science of agriculture. Two factors have contributed to the uncertainty
existing in this matter: First, the very complex and varying nature of the
compounds resulting from the decomposition of vegetable matter in the soils;
and second, the lack of uniformity in the methods of determining either the total
amount of organic matter present in a soil, or the amount that has been so far
decomposed as to be of any immediate agricultural value. Prominent among
these methods are the methods in which a combustion is resorted to, the
substance being either burned in air or in a combustion tube with some agent
supplying oxygen. The loss on ignition is no measure of the amount of organic
matter present since it is practically impossible to remove all the water from the
soil previous to ignition, and neither of the methods gives information regarding
the extent of the decomposition of the organic matter. Pure cellulose and the
black matter of a fertile soil are of very different agricultural value.
Determinations of carbon in soils by oxidation with chromic and sulfuric acid,
and with alkaline permanganate have been used. The method with alkaline
permanganate agrees fairly well with combustion with copper oxid or lead
chromate, but the chromic sulfuric acid method gives only about eighty per cent
of the carbon found by combustion processes. However valuable these processes
may be for determining the total carbon in the soil, they furnish no information
regarding the condition of the carbonaceous soil constituents, and as the
determination is really one of carbon, the organic matter must be calculated by
using an arbitrary factor. Generally the organic matter of the soil is considered to
have fifty-eight per cent carbon; yet different values are given from forty to
seventy-two per cent.
There is a general opinion that the black or dark brown material of the soil,
resulting from the decay of vegetable matter, has a much higher agricultural
value than the undecomposed vegetable matter. No very sharp dividing line can
be drawn, for changes in the soil are continually going on, and material may be
found in almost every stage between pure cellulose and carbon dioxid. The
character of the intermediate products will vary according to the conditions of
tillage and the supply of air and water.
For agricultural purposes some means of determining the amount of
decomposed matter is very desirable. Several solvents have been tried for this
purpose. The earlier attempts were made by treating the soil with successive
quantities of boiling half-saturated solution of sodium carbonate until the soil
appeared to yield no more coloring matter to the solvent. The solutions were
then united, rendered acid with HCl, which precipitated the humic acid, which
was then washed, dried, and weighed. This was considered the more soluble
portion of the humic acid. The soil was afterward treated with caustic potash
solution in the same manner, and the humus thus extracted was called insoluble
humus. This last process was really more in the nature of manufacturing humus,
for sawdust treated with caustic potash yields humic acid, and the inert organic
matter in the soil was decomposed to some extent by the caustic alkali. Neither
of the processes provided for the separation of the humic acid from the lime,
magnesia, alumina, and iron with which it is usually combined in the soil.
In case results of different workers are to be compared, it is of the greatest
importance that methods should be used that are of such a nature that errors
resulting from difference of manipulation, and from difficulty of reproducing
duplicate work can be reduced to a minimum.
Hence, a simple modification of the Grandeau method has been tried which
has the advantage of keeping a definite amount of the soil in contact with a
definite volume of ammonia for a fixed time, the strength of the ammonia
remaining constant.
The process is as follows: The soil is washed with acid and water as usual. It is
then washed into a 500 cubic centimeter cylinder with ammonia, the cylinder
closed and well shaken and allowed to remain for a definite time, usually thirty-
six hours. The material is shaken at regular intervals. The cylinder is left inclined
as much as possible without having the fluid touch the glass stopper, thus
allowing the soil to settle on the side of the cylinder and exposing a very large
surface to the action of the ammonia. During the last twelve hours the cylinder is
placed in a vertical position to allow the soil to settle well before taking out the
aliquot part of the solution.
The process of washing the soil with hydrochloric acid, water and ammonia, is
very tedious when performed in the usual way with the wash-bottle. A simple
automatic washing apparatus was devised by which a fixed volume of the
washing fluid can be delivered at regular intervals, giving ample time for the
thorough draining between each addition of the fluid, and requiring no
attention. By this apparatus work can be continued day and night. Instead of
washing on the usual form of filter paper in funnels, it is preferable with this
apparatus to hold the soils on a disk of filter paper resting on a perforated
porcelain disk in the bottom of the funnel. This removes the necessity of washing
out the filter papers, does not permit of the accumulation of humus on the edge
of the filter paper when the Grandeau process is used, and insures that all the

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General Chemistry Principles and Modern Applications

General Chemistry Principles and Modern Applications

2. The valence shell is

Whitten 10e Test Bank 1

Whitten 10e Test Bank 2

11. Which of the following statements concerning polar molecules is false?

12. Which one of the following molecules is polar?

13. Which one of the following molecules is nonpolar?

Whitten 10e Test Bank 3

Whitten 10e Test Bank 4

Whitten 10e Test Bank 5

Whitten 10e Test Bank 6

27. Which of the following statements about polar molecules is false?

30. What is (are) the bond angle(s) in BeI2 molecules?

Whitten 10e Test Bank 7

34. What is the hybridization at the boron atom in gaseous BBr3?

Whitten 10e Test Bank 8

36. Which of the following molecules has 120 bond angles?

39. Which of the following is a false statement about BF3?

Whitten 10e Test Bank 9

42. What is the hybridization at the central atom in SiH4?

Whitten 10e Test Bank 10

45. Which statement concerning the ion, SO42−, is true?

46. Which of the following statements about chloroform, CHCl3, is false?

48. Which one of the following molecules is polar?

Whitten 10e Test Bank 11

50. Which one of the following molecules is nonpolar?

51. Which one of the following molecules is polar?

53. What is the hybridization of the nitrogen atom in NH3?

Whitten 10e Test Bank 12

56. The electronic geometry of the central atom in PCl3 is ____.

57. The molecular geometry of PCl3 is ____.

Whitten 10e Test Bank 13

61. Which of the following statements about PBr3 is false?

Whitten 10e Test Bank 14

64. The molecular geometry of the hydrogen sulfide molecule is ____.

Whitten 10e Test Bank 15

69. What is the hybridization of the oxygen atom in H3O+?

Whitten 10e Test Bank 16

74. What is the hybridization at arsenic in AsF5 molecules?

75. What is the hybridization at the central atom (P) of PF3Cl2?

Whitten 10e Test Bank 17

78. Which of the following statements about AsF5 is false?

Whitten 10e Test Bank 18

81. What is the hybridization of the central I atom in I3−?

Whitten 10e Test Bank 19

88. Which one of the following molecules is polar?

Whitten 10e Test Bank 20

91. What is the hybridization at the central element in SeF6?

92. What is the hybridization at the sulfur atom in SF6?

Whitten 10e Test Bank 21

98. Which one of the following molecules is polar?